EP0044233A1 - Verfahren zur Herstellung von Pfropfcopolymerisaten aus Styrol und Kautschukpolymeren - Google Patents
Verfahren zur Herstellung von Pfropfcopolymerisaten aus Styrol und Kautschukpolymeren Download PDFInfo
- Publication number
- EP0044233A1 EP0044233A1 EP81400974A EP81400974A EP0044233A1 EP 0044233 A1 EP0044233 A1 EP 0044233A1 EP 81400974 A EP81400974 A EP 81400974A EP 81400974 A EP81400974 A EP 81400974A EP 0044233 A1 EP0044233 A1 EP 0044233A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- styrene
- norbornene
- butyl
- peroxide
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
- C08F255/06—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms on to ethene-propene-diene terpolymers
Definitions
- the present invention relates to a process for the preparation of compositions based on polymerized styrene, it relates more particularly to a process for the manufacture of graft copolymers based on styrene and of a rubbery polymer.
- Polystyrene is a thermoplastic material which, thanks to the ease with which it can be obtained and worked, is widely used in the plastics industry. Unfortunately its use is limited due to its lack of heat resistance and its poor impact resistance.
- compositions which have a very low level of grafting, that is to say a level of polystyrene grafted onto the elastomer, at most close to 2.
- observation under a microscope makes it possible to observe that the compositions obtained are made up of large rubber globules which are dispersed in the composition without any cohesion and whose size can reach 10 to 15 microns.
- composition obtained with such a dispersion does not have a fine microstructure and is therefore not very transparent and the surface appearance of the parts is defective.
- problems described above and which relate to the resistance to heat and to aging, the impact resistance, the grafting rate of polystyrene, as well as the microstructure it is necessary in order to obtain compositions exhibiting properties of interest to solve the problem of crosslinking of the elastomer.
- the present invention relates to a process for the preparation of graft copolymers formed essentially from styrene polymerized in the presence of a rubbery terpolymer of ethylene, of propylene and of a third component, characterized in that the solution is mass polymerized rubbery monomer in the presence of ditertiobutyl peroxide or benzoyl peroxide and additive chosen from divinylbenzene, triallylcyanurate and glycol acrylate.
- the implementation of the process according to the invention makes it possible to obtain grafted copolymers having a high grafting rate of between 5 and 25, as well as a good swelling index of between 5 and 22 characteristic of good crosslinking of the rubbery polymer.
- microscopic observation of the copolymers obtained according to the process of the invention makes it possible to observe that they have good cohesion and a fine microstructure such that at least 100% of the particles have a size of less than 4 microns. of which 80% at least a size less than 2 microns.
- a mixture of styrene and rubber based on ethylene, propylene and a third component is subjected to a mass polymerization step in the presence of ditertiobutyl peroxides and of additive.
- the third component which enters into the composition of the rubber used for the manufacture of the copolymers according to the invention is chosen from hexadiene - 1,4 dicyclopentadiene, tricyclopentadiene, 5-vinylnorbornene-2, 5-ethylidenenorbornene-2, -5-methylene-norbornene-2, 5 (2 propenyl) norbornene - 2, 5 (5 hexenyl) norbornene-2, 4,7,8,9 tetrahydro-indene and isopropylidene tetrahydro-indene.
- rubbers are used which have an ethylene content of 19 to 73% by weight, a propylene content of 23 to 77% and a content of 4 to 20% by weight of the third component.
- the method of the invention consists in introducing into an autoclave on the one hand the rubber based on ethylene, propylene and of third component and on the other hand the styrene optionally added with ethylbenzene.
- the autoclave used is equipped with an agitator, a heating device and a cooling system.
- the reaction mixture is heated with stirring to a temperature in the region of 40 ° C for three hours so as to dissolve the rubber in the other reagents, the quantities of which are variable.
- Styrene and ethylbenzene are used in ethylbenzene styrene weight ratios between 0 and 12%, the styrene being used in styrene weight ratios between 6 and 20 and preferably between 7 and rubber 13.
- a peroxide and an additive chosen from divinylbenzene, triallyl cyanutate or glycol acrylate are added.
- the peroxide used is benzoyl peroxide or ditertiobutyl peroxide or tertiobutyl peracetate or ditertiobutyl cyclohexane peroxide or peroxy isopropyl tertiary butyl carbonate or dicunyl peroxide or tertiobutyl perbenzoate: these peroxides can be used alone or as mixtures in amounts of between 0.1 and 0.3% by weight relative to the styrene.
- the amount of additive used is at most equal to 0.1% compared to styrene.
- antioxidants such as di-tertio-butyl-para-cresol, 2-2 'methylene bis (4 methyl- 6 tert-butylphenol), octadecyl 3- (3,5 di-butyl-4-hydroxyphenyl) propionate, tri (2 methyl 4 hydroxy: 5 tert-butyl-phenyl) butane used at most in an amount of 0.5% by weight compared to styrene.
- the polymerization is carried out at a temperature between 80 and 160 ° C for a period of approximately 8 hours. After polymerization, the polymer obtained is subjected to a heat treatment then devolatilized and granulated.
- the grafting copolymers obtained according to the process of the invention have good mechanical properties as well as good behavior under heat and aging. All of these properties, associated with their fine morphology, privilege these graft copolymers in the fields of application where excellent mechanical and physical properties are required as well as good aging and heating stability.
- the reaction mixture is stirred at 40 ° C for 3 hours. Then 0.1 parts by weight of ditertiobutyl peroxide and 0.1 parts by weight of divinylbenzene are added. The reaction mixture is then subjected to heating in stages so that its final temperature reaches 145 ° C. after 7 hours 50. After this heating phase, 81.5 parts of solid matter are obtained which are treated with hot for 1 hour 50. After devolatilization which consists in subjecting the polymer to a heat treatment at a temperature between 200 and 240 ° C under a vacuum of 730-740 mm Hg the polymer is granulated. Its characteristics are summarized in Table 1.
- the melt index is determined at 200 ° C under 5 kg.
- the impact resistance is determined according to standard ASTM D 256-73.
- the Vicat Point is determined according to standard ASTM D 1525-76: it makes it possible to express the softening point according to the pressure.
- the melt index which expresses the fluidity of the product is determined according to standard ASTM D 1238-73.
- the rate of gel which expresses the rate of grafting that is to say the amount of polystyrene grafted onto the elastomer is determined by cold stirring the graft copolymer in toluene and then centrifuging the whole, which makes it possible to determine the amount of toluene insoluble gel.
- the dry mass of the insoluble polymer is determined by treating the gel obtained previously under vacuum: the percentage of gel relative to the test portion expresses the gel rate.
- the swelling index which makes it possible to express the crosslinking rate is equal to the ratio of the mass of gel to the dry resin.
- the polymer obtained has a particle size such that 100% have a dimension of less than 2 microns.
- the particle size distribution is determined according to the electron microscopy technique described by KATO in J. Electro Micros 14 1965- (20) and which consists in using the osmium tetroxide as a developer.
- Example 1 is repeated but the addition of divinylbenzene during the polymerization is eliminated. After treatment, a polymer is obtained, the characteristics of which are summarized in Table 3.
- the table shows that the addition of divinylbenzene improves the polymer in particular with regard to its crosslinking.
- Example 1 is repeated, replacing the O, 1 part of divinylbenzene with 0.1 part of triallylcyanurate.
- Table 4 summarizes the properties of the polymer obtained.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Graft Or Block Polymers (AREA)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT81400974T ATE11553T1 (de) | 1980-07-10 | 1981-06-18 | Verfahren zur herstellung von pfropfcopolymerisaten aus styrol und kautschukpolymeren. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR8015342A FR2486530B1 (fr) | 1980-07-10 | 1980-07-10 | Procede de preparation de copolymeres greffes a base de styrene et d'un polymere caoutchouteux |
FR8015342 | 1980-07-10 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0044233A1 true EP0044233A1 (de) | 1982-01-20 |
EP0044233B1 EP0044233B1 (de) | 1985-01-30 |
Family
ID=9244063
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP81400974A Expired EP0044233B1 (de) | 1980-07-10 | 1981-06-18 | Verfahren zur Herstellung von Pfropfcopolymerisaten aus Styrol und Kautschukpolymeren |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP0044233B1 (de) |
AT (1) | ATE11553T1 (de) |
DE (1) | DE3168610D1 (de) |
FR (1) | FR2486530B1 (de) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1268588A1 (de) * | 1999-12-20 | 2003-01-02 | Samsung General Chemicals Co., Ltd. | Terpolymere des ethylens mit aromatischen vinylverbindungen und vinylnorbonen |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB896598A (en) * | 1957-06-14 | 1962-05-16 | Montedison Spa | Elastomers obtained from alpha-olefin polymers and copolymers and process for their preparation |
GB1027667A (en) * | 1963-11-14 | 1966-04-27 | Sartomer Resins Inc | Cross-linked terpolymer of ethylene propylene and non-conjugated diene exhibiting high temperature resistance to softening, stiffening or embrittlement |
FR2294205A1 (fr) * | 1974-12-09 | 1976-07-09 | Exxon Research Engineering Co | Procedede de reticulation d'elastomeres modifies |
US4007138A (en) * | 1972-05-25 | 1977-02-08 | Badische Anilin- & Soda-Fabrik Aktiengesellschaft | Manufacture of ion-exchanging shaped articles |
-
1980
- 1980-07-10 FR FR8015342A patent/FR2486530B1/fr not_active Expired
-
1981
- 1981-06-18 DE DE8181400974T patent/DE3168610D1/de not_active Expired
- 1981-06-18 EP EP81400974A patent/EP0044233B1/de not_active Expired
- 1981-06-18 AT AT81400974T patent/ATE11553T1/de not_active IP Right Cessation
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB896598A (en) * | 1957-06-14 | 1962-05-16 | Montedison Spa | Elastomers obtained from alpha-olefin polymers and copolymers and process for their preparation |
GB1027667A (en) * | 1963-11-14 | 1966-04-27 | Sartomer Resins Inc | Cross-linked terpolymer of ethylene propylene and non-conjugated diene exhibiting high temperature resistance to softening, stiffening or embrittlement |
US4007138A (en) * | 1972-05-25 | 1977-02-08 | Badische Anilin- & Soda-Fabrik Aktiengesellschaft | Manufacture of ion-exchanging shaped articles |
FR2294205A1 (fr) * | 1974-12-09 | 1976-07-09 | Exxon Research Engineering Co | Procedede de reticulation d'elastomeres modifies |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1268588A1 (de) * | 1999-12-20 | 2003-01-02 | Samsung General Chemicals Co., Ltd. | Terpolymere des ethylens mit aromatischen vinylverbindungen und vinylnorbonen |
EP1268588A4 (de) * | 1999-12-20 | 2006-03-29 | Samsung Atofina Co Ltd | Terpolymere des ethylens mit aromatischen vinylverbindungen und vinylnorbonen |
Also Published As
Publication number | Publication date |
---|---|
DE3168610D1 (en) | 1985-03-14 |
EP0044233B1 (de) | 1985-01-30 |
FR2486530B1 (fr) | 1985-05-31 |
ATE11553T1 (de) | 1985-02-15 |
FR2486530A1 (fr) | 1982-01-15 |
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